Reaction products of aldehydes and diazine derivatives



Patented July 3, 1945 v v UNITED STATES PATENT OFFICE REACTION PRODUUIS OF ALDEHYDES AND DIAZINE DERIVATIVES Gaetano F. DAlelio, Plttsfield, Masa, assi nor to General Electric Company, a corporation oi New York No Drawing. Application July 1'1, 1942, Serial No. 451,314

14 Claims.

and a diazine derivative corresponding to the following general formlua I IHR where R represents a monovalent hydrocarbon radical and R represents a member of the class consisting of hydrogen and monovalent hydrocarbon radicals.

Illustrative examples of radicals that R. and R in the above formula may represent are: aliphatic (e. g., methyl, ethyl, propyl, isopropyl, butyl, secondary butyl, isobutyl, butenyl, amyl, isoamyl, hexyl, heptyl, octyl, decyl, tetradecyl, allyl, methally], e'thallyl, crotyl, etc), including cycloaliphatic (e. g., cyclopentyl, cyclopentenyl,

cyclohexyl, cyclohexenyl, cycloheptyl, etc); aliphatic-substituted aryl (e. g., tolyl, xylyl, ethylphenyl, propylphenyl, isopropylphenyl, allylphenyl, 2-butenylphenyl, 'tertiary-butylphenyl, etc); and aryl-substituted aliphatic (e. g.,benzy1, phenylethyl, cinnamyl phenylpropyl, phenylisopro pyl, etc.). Of course it will be understood by those skilled in the art that R and R may represent any other monovalent aliphatic (e. g., alkyl, alkenyl) hydrocarbon radical or monovalent aromatic hydrocarbon radical, and that the radicals mentioned are by way of illustration and not by way of limitation. Preferably R. represents hydrogen. Instead of the hydrocarbon-substituted amino pyrimidines (1,3-diazines) represented by the above formula. corresponding derivatives of the 1,-2-diazines or of the 1,4-diazines may be employed.

The diazine derivatives used in practicing the present invention conveniently are prepared by condensing the corresponding tri-chloro (or tribromo) pyrimidine with a primary amine. This reaction may be represented by the following general equation, where R and R have the same meanings as given above with reference to Formula I:

Another suitable method of preparation comprises effecting reaction between the corresponding triamino pyrimidine and an inorganic acid mono salt of a primary amine, for example the monohydrochloride of a primary amine. This reaction may be represented by the following general equation, where R and B have the same meanings as given above with reference to Formula I:

Specific examples of diazine derivatives embraced by Formula I that may be used in producing my new compositions are listed below: 2.4,6-tri(methylamino) pyrimidine 2,4,6-tri-(methylamino) 5-me'thyl pyrimidine 2,4,6-tri-(ethylamin0) pyrimidine 2,4,6-tri-(ethylamino) 5-phenyl pyrimidine 2,4,6-tri-(phenylamino) pyrimidine 2,4,6-tri-(phenylamino) 5-phenyl pyrimidine 2,4,6-tri-(tolylamino) pyrimidine 2,4,6-tri-(allylamino) pyrimidine 2,4,6-tri- (propylamino) pyrimidine 2,4,6-tri-(isopropylamino) pyrimidine 2,4,6 -tri-(tolylamino) 5-methyl pyrimidine 2,4,6-tri-(cyclohexylamino) pyrimidine 2,4,6-tri- (cyclohexenylamino) 5-ethyl pyrimidine 2,4,6-tri-(butylamino) pyrimidine 2,4,6-tri-(pentylamino) fi-xenyl pyrimidine 8,879,691 2.4. ripr D y py mi wherein n is at least 2. 2 stands for a member of 2,4,6-tri-(naphthylamino) pyrimidine the group consisting of H and NH: and where- 2,4,8-tri-(hexyla'mino) b-hexyl pyrimidine 2,4,6-tri-(benzylamino) fi-cyciohexyi pyrimidine 2,4,6-tri-(phenethylamino) pyrimidine v 2,4,6-tri-(ethylphenylamino) pyrimidine 2,4,6-tri- (xenylamino) 5-cyclohexenyl pyrimidine 2,4,6-tri-(xylylamino) pyrimidine 2,4,6-tri-(decylamino) pyrimidine 2,4,6-tri-(tetradecylamino) pyrimidine 2,4,B-tri-(hexylamino) 5-tolyl pyrimidine 2.4,8-tri- (methylamino) 5-ethyl pyrimidine 2,4,6-tri-(ethylamino) 5-methy1 pyrimidine 2,4,6-tri- (methylamino) 5-allyl pyrimidine 8- (methylamino) 4,6-di-(ethylamino) pyrimidine 2-(ethylamino) 4,6-di- (phenylamino) pyrimidine z-(allylamino) 4,6-di-(propylamino) 5-methyl pyrimidine 2-(butylamino) 4,6-di-(allylamino) 5-pheny1pyrimidine 2,4,6-trl-(phenvlamino) 5-methallyl pyrimidine 2,4,6-tri-(tolylamino) 5-naphthyl pyrimidine 2,4,6-tri-(2'-butenylamino) pyrimidine 2,4,6-tri- (heptylamino) pyrimidine 2,4,6-tri-(isobutylamino) pyrimidine 2,4,6-trl- (isoamylam'ino) 5-isoamyl pyrimidine The present invention is based on my discovery that new and valuable materials of particular utility in the plastics and coating arts can be produced by eil'ecting reaction between ingredients comprising essentially an aldehyde, includin polymeric aldehydes, hydroxyaldehydes and aldehyde-addition products, and diazine derivatives of the kind-embraced by Formula I, numerous examples of which have been given above. Thereafter a curing reactant, specifically a chlorinated acetamide, is caused to react with this initial reaction product.

In the production of molded articles from molding compositions comprising a filled or unfilled thermosetting resin, it is highly desirable that the molding compound have a high plastic flow during molding combined with a rapid cure to an insoluble, infusible state. Surprisingly it was found that the heat-curable resinous condensation products of this invention show excellent flow characteristics during a short curing cycle. The molded articles have a high dielectric strength and very good resistance to arcing. They have a good surface ilnish and excellent resistance to water, being better, in general, than the ordinary urea-formaldehyde resins in this respect. Their water resistance also is materially better than that of resins made by reaction of tives wherein the amino radical is unsubstituted. This was quite surprising and unexpected and in no way could have been predicted. The cured resin of the present invention also have a high resistance to heat and abrasion and, therefore, are especially suitable for use where optimum heatand'abrasion-resistance are properties of primary importance.

It has been suggested heretofore that resinous condensation products be made by condensing an aliphatic aldehyde containing not more than four carbon atoms with a compound corresponding to the general formula an aldehyde with similar diazine derivain,tothecarbonatoms,areattachedmembersof the class consisting of the aforesaid NHx s ups. d ogen. y p y ny e. hydroxy, alkoxy, mercapto, thioether and substituted amino groups. A more specific example or the prior art materials coming within the above class are condensation products 'of an aliphatic aldehyde, specifically formaldehyde, with 2,4,8- triamino pyrimidine,

I NH] 6-hll1l Although such resins have valuable properties and are suitable for many applications, their water resistance is often inadequate for many electrically insulating uses and other applications of the cured resin,or of molded articles made from requires high plasticity of the molding compound during molding in order that the compound will flow rapidly and uniformly to all parts of the mold. These and other disadvantages in the materials of the above-mentioned class are avoided by using as a starting reactant a diazine derivative of the kind embraced by Formula I. The diazine derivatives used in practicing the present invention therefore are not the equivalent of the compounds embraced by Formula 1V and exemplified by 2,4,6-triamino pyrimidine (Formula V).

In practicing my invention the initial condensation reaction may be carried out at normal or at elevated temperatures, at atmospheric, subatmospheric or super-atmospheric pressures. and under neutral, alkaline or acid conditions. Preferably the reaction between the components is initiated under alkaline conditions.

. Any-substance yielding an alkaline or an acid aqueous solution may be used in obtaining alka'- line or acid conditions for the initial condensation reaction. For example, I may use an alkaline substance such as sodium, potassium or calcium hydroxides, sodium or potassium carbonates. mono-, dior tri-amines, etc. In some cases it is desirable to cause the initial condensation reaction between the components to take place in the presence of a primary condensation catalyst and a secondary condensation catalyst. The primary catalyst advantageously is either an aldehyde-non-reactable nitrogen-containing basic tertiary compound, e. g., tertiary amines such as trialkyl (e. g., trimethyl, triethyl, etc.) amines, triaryl (e. g., triphenyl, tritolyl, etc.) amines, etc.,

- or an aldehyde-reactable nitrogen-containing basic compound, for instance ammonia, primary amines (e. g., ethyl amine, propyl amine, etc.) and secondary amines (e. g., 'dipropyl amine, dibutyl amine, etc.) The secondary condensation catalyst, which ordinarily is used in an amount less than the amount of the primary catalyst. advantageously is a fixed alkali, for instance a carbonate, cyanide or hydroxide of an alkali I metal (e. g., sodium, potassium, lithium, etc.)

Illustrative examples of acid condensation catalysts that may be employed are inorganic or organic acids such as hydrochloric, sulfuric, phosphoric, acetic lactic, acrylic, malonic, etc., or acid salts such as sodium acid sulfate, monosodium phosphate, monosodium phthalate, etc. Mixtures of acids, of acid salts or of acids and of acid salts may be employed if desired.

The reaction between the aldehyde, e. g., formaldehyde, and the diazine derivative may be carried out in the presence of solvents or diluents, illlers, other natural or synthetic resinous bodies, or while admixed with other materials that also can react with the aldehydic reactant or with the diazine derivatives, e. g., urea (NHzCONHa), thiourea, selenourea and iminourea (guanidine), substituted ureas, thioureas, selenoureas and iminoureas, more particularly urea derivatives such as mentioned, for example, in my Patent No. 2,285,418, page 1 column 1, lines 41-49; monoamides of monocarboxylic acids and polyamides of polycarboxylic acids, e. g., acetamide, halogenated acetamides (e. g., a chlorinated acetamide), maleic monoamide, malonic monoamide, phthalic monoamide, maleic diamide, fumaric diamide, malonic diamide, itaconic diamide, succinic diamide, phthalic diamide, the monoamide, diamide and triamide of tricarballylic acid, etc.; aminotriazines, e. g., melamine, ammeline, ammelide, melem, melam, melon, numerous other examples being given in various copending applications of mine, for instance in my copending application Serial No. 377,524. filed February 5, 1941, and in applications referred to in said copending application; phenol and substituted phenols, e. g., the cresols, the xylenols, the tertiary alkyl phenols and other phenols such as mentioned, for example, in my Patent No. 2,239,- 441; monohydric and polyhydric alcohols, e. 2.. butyl alcohol, amyl alcohol, heptyl alcohol, octyl alcohol, 2-ethylbutyl alcohol, ethylene glycol, propylene glycol, glycerine, polyvinyl alcohol, etc.; amines, including aromatic amines, e. g., aniline, etc.; and the like.

The modifying reactants may be incorporated with the diazine derivative to form an intercondensation product by mixing all the reactants and effecting condensation therebetween or by varous permutations of reactants as described, for example, in my Patent No. 2,285 418 with particular reference to reactions involving a urea, an aliphatic aldehyde and a chlorinated acetamide. For example, I may form a partial condensation product of ingredients comprising (1) urea or melamine or urea and melamine, (2) a diazine derivative 'of the klnd'embraced by Formula I,

for instance a 2,4,6-tri-(alkylamino) pyrimidine, a 2,4,6-tri-(arylamlno) pyrimidine, a 2,4,6-tri- (alkylamino) 5-alkyl pyrimidine, a 2.4,6-tri-(alkylamino) 5-aryl pyrimidine, a 2.4,6-triarylamino) 5-a1kyl pyrimidine, a 2,4,6-tri-(arylamino) 5-aryl pyrimidine, etc., and (3) an aldehyde, including polymeric aldehydes, hydroxyaldehydes and aldehyde-addition products, for instance formaldehyde, paraiormaldehyde, glyceraldehyde, dimethylol urea, a polymethylol melamine, e. g., hexamethylol melamine, etc. Thereafter I may effect reaction between this partial condensation product and, for example, a curing reactant, specifically a chlorinated acetamide, to obtain a heat-curable composition.

Some of the condensation products of this invention are thermoplastic materials ev n at an advanced stage of condensation, while others are thermosetting or potentially thermosettlng bodies that convert under heat or under heat and pressure to an insoluble, iniusible state. The thermoplastic condensation products are 01' particular value as plasticizers for other synthetic resins. The thermosetting or potentially thermosetting resinous condensation products, alone or mixed with fillers, pigments, dyes, lubricants, plasticiaers, curing agents, etc., may be used, for example, in the production of molding compositions.

The liquid intermediate condensation products of the invention may be concentrated or diluted further by the removal or addition of volatile solvents to form liquid coating compositions 01' adjusted viscosity and concentration. The heat-convertible or potentially heat-convertible resinous condensation products may be used in liquid state, for instance as surface-coating materials, in the production of paints, varnishes, lacquers, enamels, etc., for general adhesive applications, in producing laminated articles and for numerous other purposes. The liquid heathardenable or potentially heat-hardenable condensation products also may be used directly as casting resins, while those which are of a gel-like nature in partially condensed state may be dried and granulated to form clear, unfilled heat-convertible resins.

In order that those skilled in the art better may understand how the present invention may be carried into effect, the following examples are given by way of illustration and not by way of limitation. All parts are by weight.

chloroacetamide (monochloroacetamide) 0.25

All of the above ingredients with the exception of the chloroacetamide were heated together under reflux at the boiling temperature of the mass for 20 minutes. The chloroacetamide was now added and heatin under reflux was continued for an additional 5 minutes. The resulting hot resinous syrup was mixed with 40 parts alpha cellulose in flock form and 0.2 part of a mold lubricant, specifically zinc stearic, to form a molding (moldable) compound. The wet molding composition was dried at room temperature until sufllcient moisture had been removed to provide a material that could be molded satisfactorily. A well-cured molded piece having very good water resistance was produced by molding a sample of the dried and ground molding compound for 2 minutes at C. under a pressure of'2,000 pounds per square inch. The molding compound showed very good flow characteristics during molding as evidenced bythe amount of flash on the molded piece.

Instead of using chloroacetamide (monochloroacetamide) in accelerating the curing of the potentially reactive resinous material, heat-convertible compositions may be produced by adding to the partial condensation product (in syrupy or other form) direct or active curing catalysts (e. g., citric acid, phthalic anhydride, malonic acid, oxalic acid, etc.), or latent curing catalysts (e. g., sodium chloroacetate, N-diethyl chloroacetamide, glycine ethyl ester hydrochloride, etc.) or by intercondensation with curing reactants other than monochloroacetamide (e. g., diand tri-chloroacetamldes, chloroacetonitriles, alpha,

Dimethylol urea (commercial grade containing approx. 11% by weight of water) 50.7

Aqueous ammonia (approx. 28% NHa) 3.0 Sodium hydroxide in parts water 0.2 Water 50.0 Chloroacetamide 0.5

All of the above ingredients with the exception oi' the chloroacetamide were heated together under reflux at the boiling temperature of the mass for 20 minutes. The chloroacetamide was now added and heating under reflux was continued for an additional 3 minutes. A molding compound was made from the resulting resinous syrup by mixin therewith 45 parts alpha cellulose and 0.3 part zinc stearate. The wet molding composition was dried at 60 C. for 2% hours. A wellcured molded piece having good water resistance was obtained by molding a sample of the dried and ground molding compound for 2 minutes at 150 C. under a pressure of 2,000 pounds per square inch. The molding compound showed good plastic flow during molding.

diamide. phenacyl chloride, etc.).

' A Example 2 Parts 2,4,6-tri-(methy1amino) pyrimidine 20.9

All oi the above ingredients with the exception of the chioroacetamide were heated together under reflux at boiling temperature for 30 minutes. At the end or this period of time the abovestated amount of chloroacetamide was added and molding.

Example 4 Parts 2,4,6-tri-(methylamino) pyrimidine 20.9 Para-ureido benzene and sulionamide.. 26.9 Aqueous formaldehyde 1 (approx. 37.1%

ECHO) 60.3 Aqueous ammonia (approx. 28% NHJ) 1.5 Sodium hydroxide in 1.5 parts water 0.01

were heated together under reflux at the boiling temperature 01' the mass for 8 minutes. At the end of this period of time a white resin had formed and had precipitated from the solution. This resin melted when heated on a 150 C. hot plate and would not cure to an insoluble and iniusible state in the absence of a curing agent. However.

the resin was potentially heat-curable as shown by the fact that when from 1 to 2% by weight oi glycine, chloroacetamide or other during agent such as mentioned under Example 1 was incorporated into. the resin, followed by heating on a 150 C. hot plate, the resin cured to an intusible mass.

Example 5 Parts 2,4,6-tri-(methylamino) pyrimidine 8.4 Butyl alcohol 13.5 Aqueous formaldehyde (approx. 37.1%

HUI-I0) 12.1

Sodium hydroxide in 0.5 part water 0.01

were heated together under reflux at the boiling temperature 01 the mass for 15 minutes, at the end 01' which period oi. time a white precipitate had 1 to 2% by weight 01' ing compositions. For example. it may be used in the production 'oi spirit and baking varnishes. It may be employed as a modifier oi varnishes o! the aminoplast and alkyd-resin types.

Example 6 Parts 2,4,6-tri-(methylamino) pyrimidine 8.4 Acetamide 3.0 Aqueous formaldehyde (approx. 37.1% HCHO) 20.3 Aqueous ammonia (approx. 28% NE) 0.6 Sodium hydroxide in 1 part water 0.01 were heated together under reflux at the boiling temperature 01' the mass for 15 minutes, yielding acleanresinoussyrupthatdid notcuretoan insoluble and intusible state when a sample of it was heated on a 150 C. hot plate. A thermosetting composition was obtained byincorporating into the syrupy condensation product from 1 to 2% by weight of g cine, chloroacetamide or other curing agent such as mentioned under Example 1. The cured film was relatively soft. indicating the plasticizing efl'ect'oi' the aceta-' mide on the cured composition. The properties of theresinous material ,0! this example make it particularly suitable foruse as a modifier of less plastic aminoplasts and other resinous materials oi unsatisfactory improve their plasticity.

Example 7 2,4,6-tri(methyiamino) pyrimidine Diethyl malonaie Aqueous ,i'ormaldehyde (approx. 37.1%

'HCHO) 20.3 Aqueous ammonia (approx. 26% NH3)-..-. 0.6 Sodium hydroxide in 2 parts water; 0.01

were heated together under reflux at the boiling temperature or the mass for 10 minutes, at the end or which period of time a white. resinous formed in the resulting syrup. When a sample 01 this syrup was heated on a C. hot plate it did not cure to an insoluble and iniusible other curing agent flow characteristics to solid had separated from the mass. This resinous solid was thermoplastic as indicated by the fact that it melted when a sample of it was heated on a 150 C. hot plate. The addition of from 1 to 2% by weight of glycine, chloroacetamide or other curing agent such as mentioned under Example 1 to the resinous material, followed by heating on a 150 C. hot plate, caused the resin to cure to a hard, insoluble and infusible state.

Example 8 Parts 2,4,6-trl-(methylamino) pyrimidine 8.4 Glycerine 4.6 Aqueous formaldehyde (approx. 37.1%

HCHO) 20.3 Sodium hydroxide in 1 part water 0.01

were heated together under reflux at the boiling temperature of the mass for minutes, yielding a clear, resinous syrup. This syrup was noncurlng when heated on a 135 C. hot plate, but

" cured readily to an insoluble and infusible state upon the addition of from 1 to 2% by weight of glycine, chloroacetamide or other curing agent such as mentioned under Example 1.

Example 9 Parts 2,4,6-tri-(methylamino) pyrimidine 16.7 Acrolein 16.8 Sodium hydroxide in parts water 0.02

were heated together under reflux at the boiling temperature oi. the mass for 10 minutes. The resulting resinous syrup was non-curing when a sample of it was heated on a 150 0. hot plate.

The addition of from 1 to 2% by weight of glycine, sulfamic acid, chloroacetamide or other curing agent such as mentioned under Example 1 to the resinous syrup, followed by heating on a' 150 0. hot plate, caused the resin to cure slowly to an insoluble and infusible state.

All of the above ingredients were mixed and heated under reflux at boiling temperature for 10 minutes, yielding a clear, resinous syrup. A clear, thermoplastic film was obtained when a sample of the resinous syrup was heated on a 150 C. hot plate. The addition of a small amount of a curing agent, specifically hydrochloric acid, to the resinous syrup or to the thermoplastic resin yielded a composition that cured to an insoluble and infusible state when heated on a 150 0. hot plate. The resinous composition of this example may-be used in the production of molding compounds and in the preparation of coating and impregnating compositions.

It will be understood, of course, by those skilled in the art that the reaction between the aldehyde and the diazine derivative may be efiected at temperatures ranging, for example, from room temperature to the fusion or boiling temperature of the mixed reactants or of solutions of the mixed reactants, the reaction proceeding more slowly at normal temperatures than at elevated temperatures in accordance with the general law of chemical reactions. Thus, instead of eifecting reaction between the ingredients of Examples 1 to 10, inclusive, at boiling temperature under reflux, the reaction between the components may be carried out at lower temperatures, for example at temperatures ranging from room temperature to a temperature near the boiling temperature using longer reaction periods and, in some cases, stronger catalysts and higher catalyst concentrations.

It also will be understood by those skilled in the art that my invention is not limited to condensation products obtained by reaction of ingredients comprising an aldehyde and the specific hydrocarbon substituted amino diazine named in the above illustrative examples. Thus, instead of 2,4,6-tri-(methylamino) pyrimidine, I may use 2,4,6-tri-(ethylamino) pyrimidine or other 2,4,6-tri-(alkylamino) pyrimidines, 2,4,6- tri-(phenylamino) pyrimidine (2-,4,6-tri-anilino pyrimidine), 2,4,6-tri-(tolylamino) pyrimidine (2,4,6-tri-toluid0 pyrimidine), or other 2,4,6-tri- (arylamino) pyrimidines, or any other compound of the kind embraced by Formula I, numerous examples of which have been given hereinbefore.

In producing these new condensation products the choice of the aldehyde is dependent largely upon economic considerations and upon the particulan properties desired in the finished product. I prefer to use as the aldehydic reactant formaldehyde or compounds engendering formaldehyde, e. g., paraformaldehyde, hexamethylene tetramine, etc. Illustrative examples of other aldehydes that may be employed are acetaldehyde, propionaldehyde, butyraldehyde, heptaldehyde, octaldehyde, methacrolein, crotonaldehyde, benzaldehyde, furfural, hydroxyaldehydes (e. g., aldol, glucose, glycollic aldehyde, glyceraldehyde, etc.), mixtures thereof, or mixtures of formaldehyde (or compounds engendering formaldehyde) with such aldehydes. Illustrative examples of alde- 40 hyde-addition products that may be used instead of the aldelrydes themselves are the monoand poly-(N) carbinol) derivatives, more particu larly the monoand poly-methylol derivatives of urea, thiourea, selenourea and iminourea, and of subtsituted ureas, thioureas, selenoureas and iminoureas, monoand poly-(N-carblnol) derivatives of amides of polycarboxylic acids, e. g., maleic, itaconic, fumaric, adipic, malonic, succinic, citric, phthalic, etc., monoand poly-(N- carbinol) derivatives of the aminotriazines, of the aminotriazoles, etc. Particularly good results are obtained with active methylene-containing bodies such as a methylol urea, more particularly monoand di-methylol ureas, and a methylol aminotriazine, e. g., monomethylol melamine and polymethylol melamines (di-, tri-, tetra-, pentaand hexa-methylol melamines) Mixtures of a1- dehydes and aldehyde-addition products may be employed, e. g., mixtures of formaldehyde and methylol compounds such, for instance, as dimethylol urea, trimethylol melamine, hexamethylol melamine, etc.

The ratio of the aldehydic reactant to the diazine derivative may be varied over a wide range depending upon the particular properties desired in the finished product. Ordinarily these reactants are employed in an amount corresponding to at least one mol of the aldehyde, specifically formaldehyde, for each mol of the diazine derivative. Thus, I may use, for example, from 1 to 6 or '1 or more mols of an aldehyde for each mol of the diazine derivative. When the aldehyde is available for reaction in the form of an alkylol derivative, more particularly a methylol derivative such, for instance, as dimethylol urea, trietc.0ther methylol melamine. etc., then higher amounts of such aldehyde-addition products are used, for instance from 2 or 3 up to 12 or 15 or more mois of such alkylol derivatives for each mol of the diaaine. derivative.

As indicated hereinbefore, and as further shown by a number of the examples, the Properties of-the fundamental resins of this invention may be varied widely by introducing other modifying bodies before, during or after efl'ectin'g condensation between the primary components. Thus, as modifying agents 1 may use. for examo y hy hexyl, etc. alcohols; lyhydric alcohols such, for example, as diethyleneglycol, triethylene glycol,

- pentaerythritol, etc; alcohol-ethers. e. g., ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether. diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, etc.; amides such as formamide, stearamide, acrylamide; benzene sulfonamides, toluene Phthalamide,etc.;

amines, e. g., ethylene diamine, phenylene diamin etc.; ketones, including halogenated ketones; nitriles, including halogenated nitriles, e. g., acryionitrile, methacrylonitrile, succinonitrile, chloroacetonitriles, ureas, including halogenated acylated ureas of kind described, for example, in D'Aleiio Patout No. 2,281,559; and others.

'l'hemodifyin bodiesalsomaytaketheform of high molecular weight bodies with or without resinous. characteristics, for example hydrolyzed, wood products, formalized cellulose derivatives, lignin, protein-aldehyde condensation products, aminotriazine-aldehyde condensation products. aminotriasole-aldehyde condensation products, examples of modifying bodies are the urea-aldehyde condensation products, the aniline-aldehyde condensation products, furfural condensation products, phenol-aldehyde condensation products, modified 0r unmodified, saturated or unsaturated olyhvdric alcohol-mlycarboxylic acid condensation products, water-soluble cellulose derivatives, natural gums and resins rosin, etc.: polyvinyl compounds such as polyvinyl esters, e. g., polyvinyl acetate, Polyvinyl butyrate, etc.; polyvinyl others, including polyvinyl I acetals. pecificall poylvinyl formal, etc. I Instead of effecting derivative of the kind embraced by Formula I and ganic or inorganic) of the diazine derivative or withamixture oi'thediaaine derivativeanda salt thereof. Examples or organic and inorganic acidsthatmaybeusedinthepreparationoi'such salts are hydrochloric, sulfuric, phosphoric, boric, acetic, chloroacetic. propionic, butyric, Valerie, acrylic, oxalic, Dolyacrylic, methacryiic, malonic, suecinic, adipic, malic, maleic, fumaric, benaoic, salicy i llhthalic, comphoric, etc.

Dyes, pigments, plasticizers, mold lubricants, opaciilers and various fillers er g., woo flour. glass fibers, asbestos, including deflbrated asbestoe, mineral wool, mica, cloth cuttings, etc.) may be ompounded with the resin in accordance with conventional practice to provide various thermol 'or example, in addition to their use prowl. isopropyl. isobutyl,

sulfonamides, adipic diamide,

gredim production of molding compositions, Io tri-(Phenyhmino) vactionlu'odlietof(1) a maybeusedasmodiiiersorother natural synthetic resins,aslaminatingvarnishe in production of laminated articles wherein e. g., P per, cloth, sheet asbestos, etc, arecoated andimpregnated with the resin, sn-

and thereafter united under andpressure. Theyma'ybeusedintheproducmay be employed for treating cotton, othercellulosic materialsinsheetorotherform. They also may be used as imprwnants trical mind for other electrically insulatin applications.

whatlclaimssnewanddesiretosecureby Letters Patent of the United States is:

l. A composition of matter comprising the reaction product of (l) a chlorinated acetamide with (2) the product of partial reaction of ingredients comprising an aldehyde and a compoimd to the general formula NKB where R- represents a monovalent radical and R represents amember of the class conslstingofhydrogenan monovalenthydrocarbonradieals.

1A asin claim 1 wherein the aldshyd i ormaldehyde.

asinclaimiwhereinltrcpresents .LAheat-cursble'compositionwmprisingthe vertible Mon acetamideis thasinclaimtwheresnlt' hydrogen.

8.Areslnougcomposition00mwlaingtherechlorinatedacetamide acetamide thepsoduct ofpartialreactionorhits comprising f and 2,4,6-

pyrimidine.

10. A resinous composition comprising the re- NHR action product 01' (l) a chlorinated acetamide L with (2) the product of partial reaction or ingredients comprising formaldehyde and 2,4,6-tri- 'fi (tclylamino) pyrimidine. '6 RHN. C-NHR 11. A composition comprising the reaction product of (1) a chlorinated acetamide with (2) the product of partial reaction, under alkaline Whore R represents a monovalont yd oca bo ondition f ingredients comprising urea, on radical and R represents a member of the class aldehyde and a compound corresponding to the conslstmg 01 y n and monovalent y carbon radicals. general formula NHR 14. The method of preparing new synthetic 1 compositions which comprises effecting partial reaction between ingredients comprising an al- R-C/ \N dehyde and a compound corresponding to the i general formula NHR b N (l: where It represents a monovalent hydrocarbon radical and R represents a member or the class consisting of hydrogen and monovalent hydrocarbon radicals. N 12. A composition as in claim 11 wherein R a represents hydrogen, the ald h d 1 formaldg- Where R represents a monovalent hydrocaibon hyde and the urea component i t compound radical and R represents a member of the class correspgnding to t formula qmcgm consisting of hydrogen and monovalent hydro- 13 A composition comprising the reaction carbon radicals, adding a chlorinated acetamlde product of (1) a chlorinated acetamide with (2) to h resultlog partial eact produc and t product f partial reaction, under alkaline causing the said chlorinated acetamlde to react conditions, of ingredients comprising an aminowith the Said Partial reaction P ttriazine, an aldehyde and a compound correspending to the general formula GAETANO F. D ALELIO.

CERTIFICATE OF CORRECTION.

Patent No. 2,579,691. July 5, 1915.

GAETANO F. D ALELIO.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 5, first column, line 5, after "acetic" insert a comma; line 114., for "derivatives" read -cleriva tive--; and second column line 50, for "stearic" read -stear ate--; page )4, first column, 1ine63, after "benzene" strike out "and"; page 5, second column, line 1 .2, for "poly-(N)carbino1" read'-po1y-(N-carbino1); line 1 for "subtsituted" read --substituted-; page 6, first column, line 50, for "poylvinyl" read --polyvinyl; line 614., for "comphoric" read -camphoric-; and that the said Letters Patent should be read with this correction therein that the some may conform to the record of the case in the Patent Office.

Signed andsealed this 9th day of October, A. D. 1914.5.

Leslie Frazer (Seal) First Assistant Commissioner of Patents.

10. A resinous composition comprising the re- NHR action product 01' (l) a chlorinated acetamide L with (2) the product of partial reaction or ingredients comprising formaldehyde and 2,4,6-tri- 'fi (tclylamino) pyrimidine. '6 RHN. C-NHR 11. A composition comprising the reaction product of (1) a chlorinated acetamide with (2) the product of partial reaction, under alkaline Whore R represents a monovalont yd oca bo ondition f ingredients comprising urea, on radical and R represents a member of the class aldehyde and a compound corresponding to the conslstmg 01 y n and monovalent y carbon radicals. general formula NHR 14. The method of preparing new synthetic 1 compositions which comprises effecting partial reaction between ingredients comprising an al- R-C/ \N dehyde and a compound corresponding to the i general formula NHR b N (l: where It represents a monovalent hydrocarbon radical and R represents a member or the class consisting of hydrogen and monovalent hydrocarbon radicals. N 12. A composition as in claim 11 wherein R a represents hydrogen, the ald h d 1 formaldg- Where R represents a monovalent hydrocaibon hyde and the urea component i t compound radical and R represents a member of the class correspgnding to t formula qmcgm consisting of hydrogen and monovalent hydro- 13 A composition comprising the reaction carbon radicals, adding a chlorinated acetamlde product of (1) a chlorinated acetamide with (2) to h resultlog partial eact produc and t product f partial reaction, under alkaline causing the said chlorinated acetamlde to react conditions, of ingredients comprising an aminowith the Said Partial reaction P ttriazine, an aldehyde and a compound correspending to the general formula GAETANO F. D ALELIO.

CERTIFICATE OF CORRECTION.

Patent No. 2,579,691. July 5, 1915.

GAETANO F. D ALELIO.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 5, first column, line 5, after "acetic" insert a comma; line 114., for "derivatives" read -cleriva tive--; and second column line 50, for "stearic" read -stear ate--; page )4, first column, 1ine63, after "benzene" strike out "and"; page 5, second column, line 1 .2, for "poly-(N)carbino1" read'-po1y-(N-carbino1); line 1 for "subtsituted" read --substituted-; page 6, first column, line 50, for "poylvinyl" read --polyvinyl; line 614., for "comphoric" read -camphoric-; and that the said Letters Patent should be read with this correction therein that the some may conform to the record of the case in the Patent Office.

Signed andsealed this 9th day of October, A. D. 1914.5.

Leslie Frazer (Seal) First Assistant Commissioner of Patents. 

